CN103044888B - PC composite material as well as preparation method and application thereof - Google Patents
PC composite material as well as preparation method and application thereof Download PDFInfo
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- CN103044888B CN103044888B CN201210583585.5A CN201210583585A CN103044888B CN 103044888 B CN103044888 B CN 103044888B CN 201210583585 A CN201210583585 A CN 201210583585A CN 103044888 B CN103044888 B CN 103044888B
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Abstract
The invention suitable for the field of engineering plastics provides a PC (polycarbonate) composite material as well as a preparation method and an application thereof. Aryl sulfone sulfonate of alkali metal or alkali-earth metal, a phosphate compound and a polysiloxane compound with reactive functional groups are used as flame retardants, so that the flame retardant property of the PC composite material is greatly improved, the infrared light transmittance of PC is not damaged, and the PC composite material is excellent in infrared transmittance and flame retardant property. The preparation method for the PC composite material is simple to operate and low in cost, and is very suitable for industrial production.
Description
Technical field
The invention belongs to engineering plastics field, particularly relate to a kind of PC matrix material, its preparation method and application.
Background technology
Infrared transmission material because having good infrared transparent and wider transmission wave band, and is applied in infrared imaging and guidance technology by wide sending out, as: the materials such as lens, prism, window, spectral filter.Plastics are a kind of amorphous state high molecular polymers, and some plastics have good transmitance at infrared or far infrared band, thus can be used for preparing infrared window, lens etc.Modal infrared plastics comprises: CALCIUM ACRYLATE and second) methacrylate synthetic glass, PE, PP plastics, tetrafluoroethylene, poly-tetramethyl-amylene plastics etc.; Current plastics have been widely used for the civilian or police fields such as infrared alarm, infrared monitoring and sensing.
Polycarbonate, with features such as the high transmission rate of its uniqueness, impact, dimensional stability and easy machine-shapings, occupies extremely important position at optical field.And in field of electronics, require that material has flame-retarding characteristic.At present, halogen-free flameproof has become a kind of trend in the whole world.Current, adopt the environment-friendly type polycarbonate of the fire retardant such as bromine system or phosphorus system, though flame retardant resistance is strong, want to make thinner optical goods, just need a more step to improve its flame retardant properties.In existing fire retardant systems, mainly contain phosphorus flame retardant and the large class of bromide fire retardant two, this two based flame retardant is used for PC, though greatly can strengthen the flame retardant properties of PC, reduces the infrared percent of pass of PC.When using carbon black class material to prepare black polycarbonate, because carbon black is to infrared scattering and infrared absorption partly, thus reduce infrared transmission.By the transmitance regulating the ratio between transparent red, transparent yellow, transparent blue toner and adding proportion can regulate visible ray.
Summary of the invention
In view of this, the invention provides a kind of PC matrix material, solve the technical problem of infrared transmission material flame retardant properties difference in prior art.
The present invention is achieved in that
A kind of PC matrix material, comprises the component of following weight percent:
Above-mentioned PC composite material and preparation method thereof, comprises the steps:
Polycarbonate, basic metal, the fragrant sulfone sulfonate salt flame of alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent, color and luster protective material, high temperature resistant oxidation inhibitor, lubricant, UV light absorber and toner is taken by formula;
By the fragrant sulfone sulfonate salt flame of described polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
Described color and luster protective material, high temperature resistant oxidation inhibitor, lubricant, UV light absorber and other auxiliary agent are mixed, obtains the second mixture;
By described first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material.
The present invention further provides the application of above-mentioned PC matrix material in monitor, the medium field of electronics of warning howler.
PC matrix material of the present invention, by using fragrant sulfone sulfonate, the phosphate phospho ester compound of basic metal, alkaline-earth metal, there is the polysiloxane compound of reactive functional groups as fire retardant, in other components of cooperation, the flame retardant properties of PC matrix material is greatly enhanced, and do not damage the infrared light transmission rate of PC, realize PC matrix material and there is excellent infrared transmittivity and flame retardant properties.PC composite material and preparation method thereof of the present invention, using the fragrant sulfone sulfonate of basic metal, alkaline-earth metal, phosphate phospho ester compound, having the polysiloxane compound of reactive functional groups is modifier modification polycarbonate as fire retardant, the flame retardant properties of PC matrix material is greatly enhanced, and the infrared light transmission rate of its PC does not sustain damage, and the transmitance by regulating the ratio between transparent red, transparent yellow, transparent blue toner and adding proportion can regulate visible ray.PC composite material and preparation method thereof of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of PC matrix material, comprises the component of following weight percent:
Particularly, this polycarbonate is bisphenol A-type polycarbonate, and middle height glues, and its melting index MFI is at 7 ~ 10g/10MIN, and such as, PC selects the 1250Y of Supreme Being people's production.This basic metal, the fragrant sulfone sulfonate salt flame of alkaline-earth metal is selected from diphenyl sulfide-4,4 '-disulfonate, diphenyl sulfide-4,4 '-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalate, 1-methoxynaphthalene-4-calcium sulphonate, 4-lauryl phenyl ether disulfonate, the poly-many sodium of (2,6-dimethylphenylene oxide) many sulfonic acid, the poly-many sodium of (1,3-phenylene oxide) many sulfonic acid, the poly-many sodium of (Isosorbide-5-Nitrae-phenylene oxide) many sulfonic acid, poly-(2,6-phenylbenzene phenylene oxide) many potassium of many sulfonic acid, poly-(2-fluoro-6-butyl phenylene oxide) poly-Sulfonic Lithium, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, BP-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonate, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, the formaline condensates of sodium naphthalene sulfonate, and the formaline condensates etc. of anthracene sulfonic acid sodium.Preferred sulfobenzide-3-potassium sulfonate and sulfobenzide-3,3 '-disulfonic acid dipotassium, particularly preferably their mixture.
The basic metal of this basic metal virtue sulfone sulfonate can be lithium, sodium, potassium, rubidium, caesium; The alkaline-earth metal of alkaline-earth metal virtue sulfone sulfonate can be beryllium, magnesium, calcium, strontium and barium, more preferably sylvite in basic metal.Phosphate ester flame retardants is the phosphonate ester compound that phosphniline acyl chlorides is polymerized with bisphenol compound.
The basic structure of this organo-siloxanes polymer is as follows: R
1aR
2bSiO
(4-a-b)/2; R
1be selected from alkoxyl group, hydroxyl, carboxyl, amino or sulfydryl, R
2be selected from the alkyl that carbonatoms is 1-14, wherein, 0<a≤3,0<b≤3,0<a+b≤3.Polysiloxane compound is full is enough to lower basic structure: R
1aR
2bSiO
(4-a-b)/2(1), R
1represent reactive functional groups, as: alkoxyl group, hydroxyl, carboxyl, amino, sulfydryl etc.R
2represent that carbonatoms is the alkyl of 1-14, basic structure is as (CH
3)
3siO
1/2, H (CH
3)
2siO
1/2, H
2(CH
3) SiO
1/2, (CH
3) 2 (CH
2=CH) SiO
1/2, (CH
3)
2(C
6h
5) SiO
1/2, (CH
3) (C
6h
5) (CH
2=CH) SiO
1/2deng single functionality siloxane unit; (CH
3) 2SiO, H (CH
3) SiO, H
2siO, H (C
6h
5) SiO, CH
3) (CH
2=CH) SiO, (C
6h
5)
2the two functionality siloxane units of SiO etc.; (CH
3) SiO
3/2, (C
3h
7) SiO
3/2, HSiO
3/2, (CH
2=CH) SiO
3/2, (C
6h
5) SiO
3/2deng three-functionality-degree siloxane unit.
It is desirable to finely disseminated material in melting mixing.Can be liquid, also can be pressed powder.This anti-dripping agent is tetrafluoroethylene class anti-dripping agent.Such as: this color and luster protective material of DB105 that CORIS produces is tetramethylolmethane stearate, such as, vapour bar (CIBA) company produces Irganox168.The high temperature resistant oxidation inhibitor be somebody's turn to do is 445 or 627 or both mixture.The lubricant be somebody's turn to do is TAF or PETS or both mixtures.This ultraviolet radiation absorption is the mixture of UV-5411, UV-234, UV-239, UV-3808PP5 any one or they.This toner is transparent red, transparent yellow; The compound ligand of transparent blue toner, transparent red is if the transparent red EG of: the bright Sheng of Bayer, transparent red E2G transparent yellow are as the transparent yellow HLR of dimethyl yellow, SUMITOMO CHEMICAL, the transparent yellow 6G of the bright Sheng of Bayer, transparent yellow 4G; Transparent blue is as the transparent blue 2B of the bright Sheng of Bayer, transparent blue RR, and this transparent red, transparent yellow, transparent blue toner are with equal or not etc. ratio mixing.
Further, also comprise other auxiliary agents that weight percent is 0.5-1.5%, other auxiliary agents described are selected from the mixture of thermo-stabilizer, photostabilizer, static inhibitor, releasing agent, whipping agent any one or they.PC matrix material of the present invention, by using fragrant sulfone sulfonate and the phosphate flame retardant of basic metal, alkaline-earth metal, in other components of cooperation, the flame retardant properties of PC matrix material is greatly enhanced, and do not damage the infrared light transmission rate of PC, realize PC matrix material and there is excellent infrared transmittivity and flame retardant properties.
The embodiment of the present invention provides above-mentioned PC composite material and preparation method thereof further, comprises the steps:
Step S01, supplies raw materials:
Polycarbonate, basic metal, the fragrant sulfone sulfonate salt flame of alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent, color and luster protective material, high temperature resistant oxidation inhibitor, lubricant, UV light absorber and toner is taken by formula;
Step S02, prepares the first mixture:
By the fragrant sulfone sulfonate of this polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
Step S03, prepares the second mixture:
This color and luster protective material, high temperature resistant oxidation inhibitor, lubricant and UV light absorber are mixed, obtains the second mixture;
Step S04, melt extrudes
By this first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material.
Particularly; in step S01; the fragrant sulfone sulfonate salt flame of this polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent, color and luster protective material, high temperature resistant oxidation inhibitor, lubricant, UV light absorber and toner are identical with aforementioned; do not repeat to set forth at this; further, other auxiliary agents that weight percent is 0.5-1.5% are also comprised.These other auxiliary agents are identical with aforesaid, do not repeat to set forth at this.
In step S02, the polycarbonate in step S01, basic metal, the fragrant sulfone sulfonate salt flame of alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent are mixed, obtains the first mixture
In step S03, by the color and luster protective material in step S01, high temperature resistant oxidation inhibitor, lubricant, UV light absorber, mix, obtain the second mixture;
In step S04, by the first mixture, the second mixture mixing, add toner, stir, obtain PC matrix material precursor, this precursor is melt extruded, granulation, namely obtain PC matrix material.Extrusion equipment can be singe screw or twin screw extruder, and in extrusion step, processing condition are:
One district temperature 160-180 DEG C, two district temperature 230-260 DEG C, three district temperature 250-280 DEG C, four district temperature 250-280 DEG C, five district temperature 250-280 DEG C, six district temperature 250-280 DEG C seven district temperature 260-280 DEG C, eight district temperature 270-280 DEG C, die head temperature is 280-290 DEG C, the residence time 1 ~ 2min, and pressure is 12-18MPa.
PC composite material and preparation method thereof of the present invention, the fragrant sulfone sulfonate of use basic metal, alkaline-earth metal and phosphate flame retardant are as modifier modification polycarbonate, the flame retardant properties of PC matrix material is greatly enhanced, and the infrared light transmission rate of its PC does not sustain damage, PC composite material and preparation method thereof of the present invention, simple to operate, with low cost, be very suitable for suitability for industrialized production.
The embodiment of the present invention provides the application of above-mentioned PC matrix material in monitor, warning howler further.
Below in conjunction with specific embodiment, above-mentioned PC composite material and preparation method thereof is described in detail.
Embodiment one
Embodiment of the present invention PC composite material and preparation method thereof, comprises the steps:
The component of following weight percent is provided:
By the fragrant sulfone sulfonate salt flame of this polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
This damp protective material, high temperature resistant oxidation inhibitor, lubricant and UV light absorber are mixed, obtains the second mixture;
By this first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material, the processing condition extruding process are:
One district's temperature 160 DEG C, two district's temperature 230 DEG C, three district's temperature 250 DEG C, four district's temperature 250 DEG C, five district's temperature 250 DEG C, six district's temperature 250 DEG C seven district's temperature 260 DEG C, eight district's temperature 270 DEG C, die head temperature is 280 DEG C, residence time 1min.
Embodiment two
Embodiment of the present invention PC composite material and preparation method thereof, comprises the steps:
The component of following weight percent is provided:
By the fragrant sulfone sulfonate salt flame of this polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
This damp protective material, high temperature resistant oxidation inhibitor, lubricant and UV light absorber are mixed, obtains the second mixture;
By this first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material, the processing condition extruding process are:
One district's temperature 170 DEG C, two district's temperature 240 DEG C, three district's temperature 260 DEG C, four district's temperature 260 DEG C, five district's temperature 260 DEG C, six district's temperature 260 DEG C seven district's temperature 270 DEG C, eight district's temperature 275 DEG C, die head temperature is 285 DEG C, residence time 1.5min.
Embodiment three
Embodiment of the present invention PC composite material and preparation method thereof, comprises the steps:
The component of following weight percent is provided:
By the fragrant sulfone sulfonate salt flame of this polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
This damp protective material, high temperature resistant oxidation inhibitor, lubricant and UV light absorber are mixed, obtains the second mixture;
By this first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material, the processing condition extruding process are:
One district's temperature 180 DEG C, two district's temperature 260 DEG C, three district's temperature 280 DEG C, four district's temperature 280 DEG C, five district's temperature 280 DEG C, six district's temperature 280 DEG C seven district's temperature 280 DEG C, eight district's temperature 280 DEG C, die head temperature is 290 DEG C, residence time 2min.
Performance test:
Testing standard is USS.Tensile strength standard: ASTMD638, specimen types is I type, and batten is of a size of 57mm*13mm*3.2mm (effective dimensions), and draw speed is 50mm/min; Flexural strength standard: ASTM D790, batten is of a size of 128mm*13mm*3.2mm, and rate of bending is 20mm/min; Chalpy impact standard: ASTM D256, batten is of a size of 63.5mm*12.7mm*3.2mm; Breach remains
From embodiment and comparative example comparative analysis, the physical and mechanical property is before modified substantially suitable, material is never fire-retardant change into fire-retardant, the transmittance <2% of material, material infrared transmittivity (2mm thickness) >88%. simultaneously
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a PC matrix material, comprises the component of following weight percent:
Described phosphate flame retardant is the phosphonate ester compound that phosphniline acyl chlorides is polymerized with bisphenol compound;
Described toner is the mixture of transparent red, transparent yellow, transparent blue toner, and described transparent red, transparent yellow, transparent blue toner are with equal or not etc. ratio mixing;
The basic structure of described organo-siloxanes polymer is as follows: R
1 ar
2 bsi O
(4-a-b)/2; R
1be selected from alkoxyl group, hydroxyl, carboxyl, amino or sulfydryl, R
2be selected from the alkyl that carbonatoms is 1-14, wherein, 0<a≤3,0<b≤3,0<a+b≤3;
Described anti-dripping agent is tetrafluoroethylene class anti-dripping agent, and described color and luster protective material is tetramethylolmethane stearate, and described oxidation inhibitor is 445,627 or both mixture.
2. PC matrix material as claimed in claim 1, it is characterized in that, the melting index of described polycarbonate is 7 ~ 10g/10 minute.
3. PC matrix material as claimed in claim 1, is characterized in that, the basic metal of described basic metal virtue sulfone sulfonate can be lithium, sodium, potassium, rubidium, caesium; The alkaline-earth metal of alkaline-earth metal virtue sulfone sulfonate can be beryllium, magnesium, calcium, strontium and barium.
4. PC matrix material as claimed in claim 1, it is characterized in that, described lubricant is TAF, PETS or both mixtures, described UV light absorber be UV-5411, UV-234, UV-3808PP5 any one or more, other auxiliary agents described to comprise in thermo-stabilizer, photostabilizer, static inhibitor, releasing agent, whipping agent one or more.
5. PC composite material and preparation method thereof as claimed in claim 1, comprises the steps:
Polycarbonate, basic metal, the fragrant sulfone sulfonate salt flame of alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent, color and luster protective material, high temperature resistant oxidation inhibitor, lubricant, UV light absorber and toner is taken by formula;
By the fragrant sulfone sulfonate salt flame of described polycarbonate, basic metal, alkaline-earth metal, phosphate flame retardant, polysiloxane compound, anti-dripping agent mixing, obtain the first mixture;
Described color and luster protective material, high temperature resistant oxidation inhibitor, lubricant and UV light absorber are mixed, obtains the second mixture;
By described first mixture and the mixing of the second mixture, add toner, melt extrude after mixing, obtain PC matrix material.
6. PC composite material and preparation method thereof as claimed in claim 5, is characterized in that, described in the processing condition that melt extrude be:
One district temperature 160-180 DEG C, two district temperature 230-260 DEG C, three district temperature 250-280 DEG C, four district temperature 250-280 DEG C, five district temperature 250-280 DEG C, six district temperature 250-280 DEG C, seven district temperature 260-280 DEG C, eight district temperature 270-280 DEG C, die head temperature is 280-290 DEG C, the residence time 1 ~ 2min.
7. the application of PC matrix material in monitor, warning howler as described in any one of claim 1-4.
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| CN104292872A (en) * | 2013-11-29 | 2015-01-21 | 上海智高贸易有限公司 | Plastic with flame-retardant characteristic and high transmittance within specific wavelength range, and manufacturing method thereof |
| CN103724971A (en) * | 2013-12-31 | 2014-04-16 | 上海长伟锦磁工程塑料有限公司 | Transparent halogen-free low smoke antiflaming polycarbonate composite material and preparation method thereof |
| CN105602009A (en) * | 2016-02-17 | 2016-05-25 | 黄秀茹 | Additive used for polymer and additive composition and polymer composition thereof |
| CN105601995A (en) * | 2016-02-17 | 2016-05-25 | 黄秀茹 | Additive used for polymer, additive composition and polymer composition thereof and application of additive as light stabilizer |
| CN105924926A (en) * | 2016-07-01 | 2016-09-07 | 东莞市海越塑化有限公司 | Anti-aging infrared-penetrable novel composite material and preparation method thereof |
| CN107057321A (en) * | 2017-04-20 | 2017-08-18 | 宁波浙铁大风化工有限公司 | Excellent weatherable polycarbonate material of a kind of color and preparation method thereof |
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| CN1435446A (en) * | 2002-01-28 | 2003-08-13 | 四川大学 | High-efficiency halogen-free flame-retardant polycarbonate |
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| CN101062996A (en) * | 2006-04-30 | 2007-10-31 | 佛山市顺德区高怡新塑料有限公司 | Halogen-free flame-proof weather-resisting transparent polycarbonate composition |
| CN101492566B (en) * | 2009-03-09 | 2011-11-02 | 佛山市顺德区瑞能科技有限公司 | Halogen-free flame retardant polycarbonate composition and uses thereof |
| CN101497742A (en) * | 2009-03-09 | 2009-08-05 | 佛山市顺德区瑞能科技有限公司 | Halogen-free flame-retardant composition and use thereof |
| CN101914276B (en) * | 2010-08-12 | 2013-08-07 | 东莞市信诺橡塑工业有限公司 | Polycarbonate composition and preparation method thereof |
| CN102276970B (en) * | 2011-07-04 | 2013-04-10 | 四川中物材料有限责任公司 | Halogen-free antiflaming thin-film polycarbonate material and preparation method thereof |
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